Addition products of propenoic acid amides and acidic, phosphorus- and sulfur-containing products



United States Patent ADDITION PRODUCTS OF PROPENOIC ACID AMIDES AND ACIDIC, PHOSPHGRUS- AND SULFUR-CONTAHN ING PRODUCTS John W. Bishop, Westfield, N. 1., assignor to Tidewater Oil Company, a corporation of Delaware No Drawing. Application March 17, 1954, Serial No. 416,940

3 Claims. (Cl. 260-125) The present invention relates to a novel group of chemicalcompounds having utility as oxidation-inhibitors for mineral oil compositions.

The novel compounds embodied herein are addition products of propenoic acid amides and acidic, phosphorusand sulfur-containing products of reaction between a phosphorus sulfide and a hydrocarbon or mixtures of hydrocarbons reactable with the sulfide to form acidic, phosphoru'sand sulfur-containing products.

The amide component of the addition products embodied herein may be an amide of propenoic acid or alkylsubstituted propenoic acids Which, for purposes herein, include amides of homologs' of propenoic acid, illustrated by crotonic' acid in which the alkyl substituent is on the beta-carbon atom, and amides of propenoic acid having an alkyl substituent on the alpha carbon atom of the acid, as illustrated by methacrylic acid, ethacrylic acid, and the like.

The acidic substances, containing phosphorus and sulfur, contemplated for reaction with the aforesaid amides may be selected from a variety of such substances prepared by reaction between phosphorus sulfides and hydrocarbons reactable therewith. Numerous substances of that type are known to the art and, hence, it is not considered necessary to describe such products in detail herein. For purposes of illustration, however, U. S. Patent No. 2,316,080 describes such products of reaction between phosphorus sulfides and olefin polymers; U. S. Patent No. 2,316,081 describes products of reaction between phosphorus sulfides and aromatics; and U. S. Patent No. 2,316,082 describes products of reaction between phosphorus sulfides and other types of hydrocarbons, including saturated hydrocarbons. Other suitable products of reaction between phosphorus sulfides and hydrocarbons, and useful for practice of this invention, are disclosed in copending application, Serial No. 309,152, filed September 11, 1952, now abandoned entitled, Catalyzed Phosphorus Sulfide-Hydrocarbon Reaction Products and Method of Making Same. Although still other disclosures exist pertaining to phosphorus sulfide-hydrocarbon reaction products that are acidic and contain both phosphotos and sulfur, the aforesaid specifically-referred to patents serve to show the reactivity, under a variety of conditions, between phosphorus sulfides and various types of hydrocarbons to form reaction products that are oilsoluble per se and/ or when neutralized with basic materials. The generic aspect of this invention contemplates use of such reaction products. Hence, and although the acidic reactant described hereinafter and utilized for illustrating embodiments of the invention was prepared by use of phosphorus pentasulfide and a hydrocarbon of certain type, such an acidic product has been used for purposes of illustration and not limitation.

With reference to the reaction between the stated amides and acidic reactant to form the compounds embodied herein, the amount of amide employed may be ice varied depending upon the extent to which it is desired to carry out reaction with the acidic substance. For obtaining substantially optimum conversion of the acidic substance to the amide reaction products thereof, it is preferred to employ an amount of amide sufficient to enable the reaction to proceed until substantially all of the acidic product has reacted and obtainment of such a result is facilitated by using an amount of amide theoretically sutficient to react with the acidic substance in mol to mol relationship; or an amount of amide in excess of that theoretically sufiicient to react in mol to mol relationship may be used with subsequent removal, if desired, of excess amide.

With further reference to the reaction that occurs between the stated amides and acidic, phosphorusand sulfur-containing reactants, the reaction is of the exothermic type, proceeds rapidly, and in some cases, spontaneously. Hence, exceedingly high temperatures are not only not essential, but are actually undesired as in some instances, depending upon the particular amide employed, undesired polymerization of the amide reactant may be induced. Thus, the temperature conditions for the reaction are not limitative except that, depending on the particular amide used, the reaction temperatures should be below that sufficient to induce substantial polymerization of the amide. As an illustrative embodiment, and particularly with use of lower molecular weight propenoic acid amides such as acrylamide and crotonamide, reaction temperatures of from about room temperature (e. g. 20 C.) to about C. may be employed, with more. specific illustrations being temperatures on the order of about 65 to about 90 C.

As to reaction time,.it is preferred that the reactants be maintained under reaction conditions until the reaction mixture substantially ceases to decrease in neutralization number. Generally speaking, the time required to attain such a result is not critical to the extent that a set time can be given irrespective of the particular amides, acidic substances and other conditions employed. The most suitable conditions, inclusive of reaction time, to employ can be readily determined by simple experimentation by those skilled in the art but, for most purposes, a reaction time of up to about 3 to 4 hours usually produces suitable results although in many cases the extent to which reaction occurs may be complete after onequarter of an hour.

In order to illustrate the invention, the following embodiments are set forth in which use is made, by way of example, of a furfural extract-Pass reaction product as the acidic, phosphorusand sulfur-containing reactant. The furfural extract employed was obtained as an extract in selective solvent (furfural) refining of a Penn Neutral oil, said extract being characterized by having the following properties: Specific extinction coefiicient of 58.8 at 2600 A; viscosity (SUS) of 73.8 at 210 F.; gravity of 80 API; and an average molecular weight of 316. In preparing the acidic reactant, a reaction mixture was prepared comprising 30 grams of phosphorus pentasulfide and 360 grams of the aforedefined exrract as the hydrocarbon component. The mixture was heated for two hours at C.-with vigorous stirring, followed by diluting the reacted mixture with hexane, filtering to remove sludge and unreacted material, and removal of hexane from the filtrate. The resulting product was a dark-colored, viscous (of syrupy consistency) material having a neutralization number of 28.18, a sulfur content of 4.05%, and a phosphorus content of 1.63%.

Example I A mixture was prepared consisting of 30 grams of the aforedescribed acidic, phosphorusand sulfur-containing product and 1.07 grams of acrylamide, i. e. an amount of acrylamide theoretically sufiicient to react in substantially mol to mol relationship with the acidic reactant.

The mixture was heated at 85 C. for two hours with vigorous stirring,'during which time no evidence of byproduct formationwas observed, to produce a product of addition reaction between the stated reactants, said addition product being a viscous, homogeneous, dark-colored liquid soluble in mineral oil and having a neutralization number of 12.66, a sulfur content of 3.66%, and a phosphorus content of 1.29%.

. Example 11 Example 111 A reaction mixture was prepared comprising 30 grams of the aforedescribed acidic reactant and 1.28 grams of crotonamide. Themixture was heated at 85 C. for

2 hours with. vigorous stirring, during which time no evidence of by-produet formation was observed, to produce a product of addition reaction between the stated reactants, said addition product being a viscous homogeneous, dark-colored liquid soluble in mineral oil and having a neutralization number of 14.66, a sulfur content of 3.89%, and a phosphorus content of 1.48%.

Example IV A reaction mixture was prepared using the same reactants,'and amounts thereof as in Example III but differ ing therefrom in that the reaction mixture was heated for four hours at85" C. The reaction product had a neutralization number of 13.94, a sulfur content of 3.75%,

t 4 V V a phosphorus content of 1.41% and otherwise was similar to the addition product of Example 111.

The novel addition products embodied herein are useful as additives for mineral oil compositions to impart antioxidant properties thereto. Such a utility for the novel products is more fully described in my copending application, Serial No. 331,497, filed January 15, 1953, relating to mineral oil compositions containing compounds such as embodied herein.

Although the present invention has been described in conjunction with certain preferred embodiments thereof, those skilled in the art will readily recognize that variations and modifications can be made. Such modifications and variations are to be considered to be within the purview. of the specification and scope of the appended claims.

I claim:

1. An addition product of an amide from the group consisting of acrylamide and crotonamide and an acidic,

V phosphorousand sulfur-containing product of reaction between phosphorous pentasulfide and a furfural extract from a petroleum lubricating oil fraction. r

2. The product of claim 1 wherein the amide is acrylamide.

3; The product of claim 1 wherein the amide is crotonamide.

References Cited in the file of this patent UNITED STATES PATENTS 2,593,496 Smith et al Apr. 22, 1952 2,658,062 Jones Nov. 3,1953

2,673,196 Hughes et a1. Mar. 23, 1954.

OTHER REFERENCES Houben-Weyl: Methods of Organic Chemistry, vol. IV,

. Acid Compounds 111, pages 672-3. 

